CN103071480B - Erbium gadolinium antimony-based composite magnetic particle photocatalyst with core-shell structure, preparation and application - Google Patents
Erbium gadolinium antimony-based composite magnetic particle photocatalyst with core-shell structure, preparation and application Download PDFInfo
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- CN103071480B CN103071480B CN201210433808.XA CN201210433808A CN103071480B CN 103071480 B CN103071480 B CN 103071480B CN 201210433808 A CN201210433808 A CN 201210433808A CN 103071480 B CN103071480 B CN 103071480B
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- 239000006249 magnetic particle Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title abstract description 8
- 239000011941 photocatalyst Substances 0.000 title abstract description 8
- GBRSYKHFITZFOY-UHFFFAOYSA-N [Sb].[Gd].[Er] Chemical compound [Sb].[Gd].[Er] GBRSYKHFITZFOY-UHFFFAOYSA-N 0.000 title abstract description 3
- 239000011258 core-shell material Substances 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 158
- 239000000463 material Substances 0.000 claims abstract description 87
- 239000002245 particle Substances 0.000 claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000843 powder Substances 0.000 claims description 65
- 238000006555 catalytic reaction Methods 0.000 claims description 54
- 229910001566 austenite Inorganic materials 0.000 claims description 51
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 48
- 230000005303 antiferromagnetism Effects 0.000 claims description 33
- 230000005298 paramagnetic effect Effects 0.000 claims description 31
- 230000001699 photocatalysis Effects 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 18
- 230000005611 electricity Effects 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 240000002853 Nelumbo nucifera Species 0.000 claims description 8
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 8
- 235000006510 Nelumbo pentapetala Nutrition 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000009881 electrostatic interaction Effects 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229920006229 ethylene acrylic elastomer Polymers 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 230000008961 swelling Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 abstract description 30
- 229910052724 xenon Inorganic materials 0.000 abstract description 26
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000001257 hydrogen Substances 0.000 abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 23
- 239000002351 wastewater Substances 0.000 abstract description 17
- 238000000354 decomposition reaction Methods 0.000 abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011521 glass Substances 0.000 abstract description 4
- 230000005307 ferromagnetism Effects 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052753 mercury Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 abstract 1
- 230000005291 magnetic effect Effects 0.000 description 73
- 239000007864 aqueous solution Substances 0.000 description 43
- 229910052799 carbon Inorganic materials 0.000 description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 39
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 28
- 230000015556 catabolic process Effects 0.000 description 28
- 238000006731 degradation reaction Methods 0.000 description 28
- 229960000907 methylthioninium chloride Drugs 0.000 description 28
- 230000005855 radiation Effects 0.000 description 27
- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 description 25
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 25
- CZIRZNRQHFVCDZ-UHFFFAOYSA-L titan yellow Chemical compound [Na+].[Na+].C1=C(C)C(S([O-])(=O)=O)=C2SC(C3=CC=C(C=C3)/N=N/NC3=CC=C(C=C3)C3=NC4=CC=C(C(=C4S3)S([O-])(=O)=O)C)=NC2=C1 CZIRZNRQHFVCDZ-UHFFFAOYSA-L 0.000 description 23
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 23
- 230000008878 coupling Effects 0.000 description 20
- 238000010168 coupling process Methods 0.000 description 20
- 238000005859 coupling reaction Methods 0.000 description 20
- 230000000593 degrading effect Effects 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000005294 ferromagnetic effect Effects 0.000 description 19
- 238000005273 aeration Methods 0.000 description 14
- 230000033558 biomineral tissue development Effects 0.000 description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 11
- 239000008187 granular material Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 238000013459 approach Methods 0.000 description 7
- 239000007857 degradation product Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- -1 hydroxyl radical free radical Chemical class 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KQHKSGRIBYJYFX-UHFFFAOYSA-J Ponceau S Chemical compound [Na+].[Na+].[Na+].[Na+].Oc1c(cc2cc(ccc2c1N=Nc1ccc(cc1S([O-])(=O)=O)N=Nc1ccc(cc1)S([O-])(=O)=O)S([O-])(=O)=O)S([O-])(=O)=O KQHKSGRIBYJYFX-UHFFFAOYSA-J 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 230000005426 magnetic field effect Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to an erbium gadolinium antimony-based composite magnetic particle photocatalyst with core-shell structure, a preparation and an application. A structural formula of a photocatalyst material is Gd3-xErxSbO7 (0.5<=x<=1), the particle size is 0.04-0.32 micrometers. Gamma-Fe2O3 ferromagnetism particle core-Gd3-xErxSbO7 (0.5<=x<=1), SiO2Gd3-xErxSbO7 (0.5<=x<=1) and MnO-Gd3-xErxSbO7 (0.5<=x<=1) are used; the particle size of Gamma-Fe2O3, SiO2 and MnO is 0.06-1 micrometer, and the particle size of Gd3-xErxSbO7 (0.5<=x<=1) after being wrapped with the core is 0.09-1.30 micrometer. The above material are respectively loaded with a Pt, NiO or RuO2 auxiliary catalyst; the auxiliary catalyst mass ratio is 20-30%, the light source is an xenon lamp or high pressure mercury lamp, and the water decomposition is carried out in an enclosed glass piping internal illumination reactor controlled by a plurality of valves to prepare hydrogen or degrade waste water.
Description
Technical field
The present invention relates to a kind of novel photocatalyst, preparation and application, especially powder catalytic material Gd
3-xer
xsbO
7γ-the Fe of (0.5≤x≤1) and " magnetic-particle core-photochemical catalyst shell " structure
2o
3-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2-Gd
3-xer
xsbO
7(0.5≤x≤1), MnO-Gd
3-xer
xsbO
7(0.5≤x≤1), preparation technology, the application of removing the organic pollution in water body through photocatalysis, and the application of photochemical catalyzing hydrogen making.
Background technology
Along with economic development, water environment pollution problem is day by day serious in recent years.In water body environment, the processing that is difficult to biodegradable organic pollution is difficult point and the hot subject in water treatment field always.Being difficult to biodegradable organic pollution has great harm to the health of human body, and ecological environment is had to huge destruction, therefore should find good technology and technique and remove this pollutant in water body.Due to poor removal effect or the basic non-processor effect of routine biochemistry processing method to this class material, must adopt photocatalytic advanced oxidation technology and novel photocatalysis material to remove targetedly it.About the research and development of novel photocatalysis material, come into one's own year by year.As everyone knows, solar spectrum medium ultraviolet luminous energy is less than 5%, and the visible ray that wavelength is 400-750nm accounts for nearly 43%.Can not effectively utilize visible ray if utilize catalysis material to solve water pollution problem, the meaning existing as the catalysis material that solves problem of environmental pollution can weaken greatly.And with regard to the depollution of environment, also will be restricted for the indoor application that there is no ultraviolet light.In addition the energy hydrogen that, adopts cheap cost to prepare novel clean is also current hot subject.Based on this, in order to effectively utilize sunshine, we wish that exploitation has the catalysis material of photocatalytic activity under visible ray, thereby solve extremely urgent water environment pollution and energy scarcity problem.
For the exploitation of visible-light response type surround lighting catalysis material, one of its main flow is under UV-irradiation, to show highly active TiO
2in with doping dissimilar metal and make it to there is visible light-responded research.Another main flow is that to explore band gap width narrow and have a non-oxidized substance semiconductor of absorption characteristic in visible region.Typically there are the sulfur family such as cadmium sulfide, cadmium selenide metallic compound and organic material etc.But the oxidized dissolving due to the effect of the electrified cavity generating under illumination of these materials, exists and there is no the problems such as stable function.Therefore, wish research and development under illumination its structure and photoelectrochemical property all stable compound carry out degradation water internal pollution thing as catalysis material.The research that utilizes these powder photocatalytic materials and solar energy to degrade organic pollution in water body or to decompose toxic pollutant causes scientists keen interest, with regard to purifying contaminated water body environment, these conductor oxidate photocatalytic powder materials will be played the part of extremely important role in future.
The fundamental design idea of novel visible responsive photocatalytic material is to control crystal structure and electronic state.Its photocatalysis principle is in the time that the illumination that energy is greater than semiconductor energy gap is mapped on semiconductor, Electron absorption luminous energy in semiconductor valence band is excited on conduction band, thereby on conduction band, produce electronegative high activity electronics, in valence band, produce the hole of positively charged, form light induced electron and the right redox system of photohole.Have an effect in dissolved oxygen, water, electronics and hole, final generation has highly chemically active hydroxyl radical free radical, utilize the hydroxyl radical free radical of this high activity can oxidize water in multiple hardly degraded organic substance be CO
2with little molecule inorganic matters such as water; Or utilizing the photohole in valence band with strong oxidability, can be the inorganic matters such as carbon dioxide and water rapid organic matter oxidation Decomposition.Thereby can be used for organic pollution in the depollution of environment and degraded water body.Therefore, be the efficiency that improves oxide semiconductor film material degradation organic pollutants in water body, the forbidden band of oxide semiconductor film material should be enough narrow, and the light induced electron forming after solar light irradiation and photohole compound to being not easy.
Japan carry out TiO since the eighties
2catalysis material is applied to the research of purifying water process, but because photocatalytic oxidation degradation water pollutant is the three-dimensional planar reaction of carrying out on catalysis material surface, pulverous TiO
2photocatalytic powder material is difficult to separate from water after water treatment, reclaims and reuses difficulty.Based on this, it is particularly important that the research of film-form catalysis material just seems, can avoid the secondary pollution of water in contaminated water body purification process.And utilize the degrade rarely seen report of research of organic pollution in water body of oxide semiconductor film catalysis material.In recent years, scientists, aspect the research of novel visible catalysis material, has obtained a lot of achievements: adopt Bi
12geO
20the powder organic matters such as methyl orange of effectively degrading; Adopt Co
3o
4/ BiVO
4can degradation of phenol; Adopt Ta
3n
5particle can degradation of methylene blue dyestuff; Adopt Na
2ta
2o
6the congo red of can degrading; Adopt Bi
2gaTaO
7can degradation of methylene blue dyestuff; Adopt Fe
0.9ni
0.1taO
4with visible ray can decomposition water hydrogen making.LaFeO prepared by Fu Xixian
3, LaFe
1-xcu
xo
3(x=0.02,0.05) has less band gap, can effectively utilize visible ray to carry out photocatalytic degradation to the organic matter in water.Zou Zhi has just waited people successfully to synthesize CaBi
2o
4deng novel photocatalysis material, utilize CaBi
2o
4deng novel photocatalysis material and visible ray degradation water and airborne formaldehyde, acetaldehyde, methylene blue and H effectively
2the nuisances such as S.Zhu Yongfa, Zhao Jincai etc. utilize homemade new material (as Bi
2wO
6deng) rhodamine B in the water of fast and effeciently having degraded, its effect is greatly improved compared with conventional method.Luan Jing flies seminar and has successfully prepared first Ga
2biTaO
7powder photocatalytic degradation water body Methylene Blue dyestuff, after 140 minutes, methylene blue is completely degraded.Therefore, the photoresponse scope of expansion catalysis material is to improve effective ways of photocatalysis quantum efficiency.In addition; adopting novel visible responsive photocatalytic material, can make full use of in solar spectrum 43% visible ray, is hydrogen and oxygen by water decomposition; and then obtain hydrogen energy source clean, non-secondary pollution, alleviate oil and natural gas and be about to the exhausted energy crisis of bringing.Utilize these above-mentioned hydrogen energy source can prepare the energy source and power of fuel cell for the vehicles such as electric automobile and electric bicycle.Mostly the visible-light photocatalysis material of reporting is at present powdered, in suspension system, there is good photocatalytic activity, in addition, in order to solve the secondary pollution problem of Powdered catalysis material in suspension system, urgent need is prepared nucleocapsid sprills shape catalysis material, object is intended to improve the rate of recovery of nucleocapsid sprills shape catalysis material, also ensures that nucleocapsid sprills shape catalysis material has high photocatalysis quantum efficiency simultaneously.
In sum, adopt novel catalysis material, under radiation of visible light, the organic pollution that not only can degrade in water body, can also prepare clean hydrogen energy source, has both solved to a certain extent problem of environmental pollution, has also solved energy crisis.Therefore, organic pollution or decomposition water hydrogen making that therefore development of new catalysis material is removed in water body not only can produce significant economic benefit, and can also produce huge environmental benefit and social benefit.
Summary of the invention
The object of the invention is: propose a kind of powder catalytic material Gd
3-xer
xsbO
7(0.5≤x≤1) and preparation were established and method, performance characterization and application.And the γ-Fe of a kind of " magnetic-particle core-photochemical catalyst shell " structure of proposition
2o
3(ferromagnetic particle core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Gd
3-xer
xsbO
7(photochemical catalyst shell) preparation technology, performance characterization and application.Especially adopt the oxide material of rare earth Er to there is better effect.
Technical scheme of the present invention is: powder catalytic material, and as following structural formula: Gd
3-xer
xsbO
7(0.5≤x≤1), the particle diameter of powder is 0.04-0.32 micron.
Catalysis material γ-the Fe of nucleocapsid structure
2o
3(ferromagnetic particle core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell).γ-Fe
2o
3, SiO
2with the particle diameter of MnO be 0.06-1 micron, Gd
3-xer
xsbO
7after (0.5≤x≤1) parcel core, particle diameter is 0.09-1.30 micron.
The application of powder catalytic material or nucleocapsid structure catalysis material, passes through Gd
3-xer
xsbO
7(0.5≤x≤1) powder is catalyst, or difference supporting Pt, NiO or RuO
2(lower-cost scheme is cocatalyst: the NiO or the RuO that add 20-30% mass ratio
2particle or powder and Gd
3-xer
xsbO
7evenly mixed), light source is xenon lamp or high-pressure sodium lamp, in the airtight glass piping interior lighting reactor by multiple valve controls, carries out decomposition water hydrogen making or degrading waste water.
The application of the catalysis material of nucleocapsid structure, the organic pollution titan yellow (C in the reaction system degrading waste water forming by magnetic field device and nucleocapsid structure catalysis material
28h
19n
5na
2o
6s
4), aniline blue (C
32h
25n
3na
2o
9s
3), the green B (C of diaminourea
34h
22n
8na
2o
10s
2), core fast red (C
14h
8nNaO
7s), Ponceau S (C
22h
12n
4na
4o
13s
4), methylene blue (C
16h
18clN
3s) etc., magnetic field device is the adjustable alternating magnetic field generator of intensity, and magnetic field intensity is chosen 0.5～5T (tesla), and light source is xenon lamp or high-pressure sodium lamp; Adopt the catalysis material γ-Fe of nucleocapsid structure
2o
3(ferromagnetic particle core)-Gd
3-xer
xsbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
3-xer
xsbO7 (photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
3-xer
xsbO
7(photochemical catalyst shell), as catalyst, (cost scheme lower and better effects if is above-mentioned three kinds of magnetic coupling catalysis materials: the NiO or the RuO that add 20-30% mass ratio
2particle or powder and Gd
3-xer
xsbO
7evenly mixed) percent by volume respectively account for volume ratio and be 1/3rd, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in the aqueous solution, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution, adopt edge filter (λ >420nm), and adopt oxygenic aeration simultaneously.Whole illumination reaction carries out under airtight lighttight environment.
The catalysis material magnetic-particle core-Gd of nucleocapsid structure
3-xer
xsbO
7the preparation method of (0.5≤x≤1): adopt the method for electrostatic interaction to prepare hud typed complex microsphere: the Gd modifying by lotus positive electricity ethylene-acrylic rubber AEM
3-xer
xsbO
7ferromagnetic particle γ-the Fe of (0.5≤x≤1) and bear electricity
2o
3, paramagnetic particle SiO
2or anti-ferromagnetism particle MnO interacts; Adopt micron-sized powder photocatalytic material Gd
3-xer
xsbO
7(0.5≤x≤1), AEM (ethylene-acrylic rubber), Nanoscale Iron magnetic-particle γ-Fe
2o
3, paramagnetic particle SiO
2or anti-ferromagnetism particle MnO; To be powder photocatalytic material Gd
3-xer
xsbO
7quality 2-5 nanometer γ-Fe doubly
2o
3, SiO
2or the water that MnO is placed in respectively 500-1000 part quality stirs, add weak aqua ammonia 1-8 part, make nanometer γ-Fe
2o
3, SiO
2or MnO bear electricity, add weak aqua ammonia, make oxide surface absorption OH
-and with negative electrical charge.For subsequent use; Get 0.1g powder photocatalytic material Gd
3-xer
xsbO
7(0.5≤x≤1), with the ethanolic solution dipping stirring of AEM concentration 2-9%w/w, makes Gd
3-xer
xsbO
7(0.5≤x≤1) lotus positive electricity, then use the nanometer γ-Fe of above-mentioned configuration
2o
3, SiO
2or the mixed stirring of MnO ammoniacal liquor mixed solution is swelling, makes electronegative nanometer γ-Fe
2o
3, SiO
2or MnO is by the Gd of the AEM modification of electrostatic interaction and lotus positive electricity
3-xer
xsbO
7(0.5≤x≤1) is at Gd
3-xer
xsbO
7(0.5≤x≤1) surface forms shell structure, and the thickness of shell can be according to the nanometer γ-Fe adding
2o
3, SiO
2or the amount of MnO decides, and then use absolute ethyl alcohol successively, deionized water cyclic washing, remove unnecessary AEM ethanolic solution and ammonia spirit, room temperature is dried, and must have the catalysis material magnetic-particle core-Gd of nucleocapsid structure
3-xer
xsbO
7(0.5≤x≤1).
The invention has the beneficial effects as follows: successfully prepare powder catalytic material Gd by adopting the method for electrostatic interaction to prepare hud typed complex microsphere
3-xer
xsbO7 (0.5≤x≤1) has prepared the γ-Fe of novel " magnetic-particle core-photochemical catalyst shell " structure simultaneously
2o
3(ferromagnetic particle core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
3-xer
xsbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell).And it is carried out to a series of signs, study the above-mentioned novel photocatalysis material contaminated Organic Pollutants In Water of degrading and (comprised titan yellow under visible ray or UV-irradiation, aniline blue, the green B of diaminourea, core fast red, Ponceau S, methylene blue) efficiency and mechanism of degradation, efficiency and the optical activity of research decomposition water hydrogen making under visible ray or UV-irradiation, by magnetic field-light-catalyzed reaction system, promote the gradient of composite magnetic catalysis material in organic wastewater to distribute, also promoted being uniformly distributed of magnetic coupling catalysis material simultaneously, and then promote fully contacting of light source and organic pollution, greatly improve the degradation efficiency of organic pollution.The present invention especially adopts the oxide material of rare earth Er to have better effect: final beneficial effect is to make the clearance of above-mentioned organic pollution reach NiO or the RuO of the auxiliary 20-30% mass ratio of 99.9%(
2), above-mentioned organic pollution total organic Carbon removal reaches 99.5%.
Brief description of the drawings
Fig. 1 is Gd of the present invention
2erSbO
7transmission electron microscope collection of illustrative plates.
Fig. 2 is Gd of the present invention
2erSbO
7actual measurement XRD collection of illustrative plates.
Fig. 3 is Gd of the present invention
2erSbO
7band structure.
Detailed description of the invention
Prepare powder catalytic material Gd
3-xer
xsbO
7(0.5≤x≤1); In addition γ-the Fe of preparation " magnetic-particle core-photochemical catalyst shell " structure,
2o
3(ferromagnetic particle core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
3-xer
xsbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell).
(1) preparation can be at the novel photocatalyst Gd of visible light wave range or the response of ultraviolet light wave band
3-xer
xsbO
7(0.5≤x≤1); Preparation can be at the γ-Fe of novel " magnetic-particle core-photochemical catalyst shell " structure of visible light wave range or the response of ultraviolet light wave band
2o
3(ferromagnetic particle core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
3-xer
xsbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell).The absorption spectra that adopts ultraviolet-visible spectrophotometer and UV-Vis DRS spectrometer to produce under visible ray (or ultraviolet light) irradiates the new catalyst of above-mentioned preparation is measured, and has characterized its optical absorption property.Measure above-mentioned new catalyst x-ray photoelectron power spectrum (XPS), inquire into the electron structure feature on above-mentioned new catalyst surface and the transport mechanism in electronics and hole in catalyst crystal under magnetic fields, analyzed the each microregion element composition of catalyst of magnetic-particle area load, and binding isotherm result of calculation level structure and the density of electronic states of above-mentioned new catalyst are analyzed.
(1-1) powder catalytic material Gd
3-xer
xsbO
7the preparation of (0.5≤x≤1): adopt the method for high temperature solid-phase sintering to prepare Gd
3-xer
xsbO
7(0.5≤x≤1) photocatalytic powder material; Er taking purity as 99.99%
2o
3, Gd
2o
3and Sb
2o
5for raw material, the Er by Er, Gd and Sb with the atomic ratio of described molecular formula
2o
3, Gd
2o
3and Sb
2o
5fully mix, then in grinding in ball grinder, the particle diameter of powder reaches 1.3-1.7 micron, dries 3 ± 1 hours at 200 ± 30 DEG C, and compacting in flakes, is put into high temperature sintering furnace and fired.Furnace temperature is risen to 700 ± 30 DEG C, be incubated cooling with stove after 7 ± 2 hours, it is 1.2-1.5 micron that pressed powder taking-up is crushed to particle diameter, then by blocks these powder compaction, puts into high temperature sintering furnace sintering, the highest furnace temperature is 750 ± 20 DEG C, be incubated coolingly with stove after 7 ± 1 hours, pressed powder taken out to be crushed to particle diameter be 1.2-1.4 micron, then by blocks these powder compaction, put into high temperature sintering furnace sintering, Elevated Temperature Conditions is as follows:
A. be warming up to 400 DEG C by 20 DEG C, the heating-up time is 40 ± 10min; B. at 400 DEG C of insulation 60 ± 10min; C. be warming up to 780 DEG C by 400 DEG C, the heating-up time is 60 ± 10min; D. at 780 DEG C of insulation 440-820min; E. be warming up to 1320 ± 10 DEG C by 780 DEG C, the heating-up time is 50 ± 10min; F. at 1320 ± 10 DEG C of insulation 4000 ± 200min, stove is cold.
Pressed powder is cooling with stove after 1320 ± 10 DEG C of insulation 4000 ± 200min of maximum temperature, and it is 0.04-0.32 micron that taking-up pressed powder is crushed to particle diameter, is finally successfully prepared pure Gd
3-xer
xsbO
7(0.5≤x≤1) powder photocatalytic material.
(1-2) carry out the catalysis material magnetic-particle core-Gd of nucleocapsid structure according to above-mentioned powder catalytic material
3-xer
xsbO
7the preparation of (0.5≤x≤1): adopt the method for electrostatic interaction to prepare hud typed complex microsphere: the Gd modifying by lotus positive electricity ethylene-acrylic rubber AEM
3-xer
xsbO
7ferromagnetic particle γ-the Fe of (0.5≤x≤1) and bear electricity
2o
3, paramagnetic particle SiO
2or anti-ferromagnetism particle MnO interaction, make the catalysis material magnetic-particle core-Gd with nucleocapsid structure
3-xer
xsbO
7(0.5≤x≤1).
Material: sol-gel process is prepared powder photocatalytic material Gd
3-xer
xsbO
7(0.5≤x≤1), AEM (ethylene-acrylic rubber), Nanoscale Iron magnetic-particle γ-Fe
2o
3, paramagnetic particle SiO2 or anti-ferromagnetism particle MnO.
(thickness of the shell that can produce as requested of quality adds, and is generally powder photocatalytic material Gd by a certain amount of
3-xer
xsbO
72 or 5 times) nanometer γ-Fe
2o
3, SiO
2or MnO is placed in 100ml water and stirs, add weak aqua ammonia 2 or 8ml, make nanometer γ-Fe
2o
3, SiO
2or MnO bear electricity, for subsequent use; Get 0.1g powder photocatalytic material Gd
3-xer
xsbO
7(0.5≤x≤1), with the AEM ethanolic solution dipping stirring of finite concentration (2%w/w or 9%w/w), makes Gd
3-xer
xsbO
7(0.5≤x≤1) lotus positive electricity, then use the nanometer γ-Fe of above-mentioned configuration
2o
3, SiO
2or the mixed stirring of MnO ammoniacal liquor mixed solution is swelling, makes electronegative nanometer γ-Fe
2o
3, SiO
2or MnO is by the Gd of the AEM modification of electrostatic interaction and lotus positive electricity
3-xer
xsbO
7(0.5≤x≤1) is at Gd
3-xer
xsbO
7(0.5≤x≤1) surface forms shell structure, and the thickness of shell can be according to the nanometer γ-Fe adding
2o
3, SiO
2or the amount of MnO decides, and then use absolute ethyl alcohol successively, deionized water cyclic washing, remove unnecessary AEM ethanolic solution and ammonia spirit, room temperature is dried, and must have the catalysis material magnetic-particle core-Gd of nucleocapsid structure
3-xer
xsbO
7(0.5≤x≤1).
(1-3) method for building up of magnetic field-light-catalyzed reaction system
The application of the catalysis material of nucleocapsid structure, the reaction system degrading waste water forming by magnetic field device and catalysis material, magnetic field device is the adjustable alternating magnetic field generator of intensity, and magnetic field intensity is chosen 0.3～5T (tesla), and light source is xenon lamp or high-pressure sodium lamp; Adopt γ-Fe
2o
3(ferromagnetic particle core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
3-xer
xsbO
7(0.5≤x≤1) (photochemical catalyst shell) is as catalyst, the percent by volume of above-mentioned three kinds of magnetic coupling catalysis materials respectively accounts for 1/3rd, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in the aqueous solution, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution, adopt edge filter (λ >420nm), and adopt oxygenic aeration simultaneously.Whole illumination reaction carries out under airtight lighttight environment.Magnetic field intensity also can be 0.05～5T (tesla).Light source is 300W xenon lamp and 400W high-pressure sodium lamp.In selection water, typical hardly degraded organic substance titan yellow, aniline blue, the green B of diaminourea, core fast red, Ponceau S, methylene blue are as target degradation product.
Control composite magnetic particle containing distribution gradient in the organic aqueous solution by magnetic field, utilize the coated novel photocatalyst of magnetic-particle core of different magnetic (ferromagnetism, paramagnetism and anti-ferromagnetism), these magnetic coupling catalysis materials can promote the mixing of similar magnetic-particle under directional magnetic field effect, avoid particle agglomeration, make magnetic coupling catalysis material be evenly distributed on upper, middle and lower-ranking in the aqueous solution thereby it is evenly dispersed in the aqueous solution completely.Also can apply flexibly as required magnetostatic field and alternating magnetic field, can in very large space and composition range, adjust easily the distribution of ferromagnetism and sub magnetic debris, and then the surface coated photochemical catalyst of magnetic-particle can fully be contacted with organic pollution and light source, under visible ray (or ultraviolet light) irradiates, organic pollution can be degraded expeditiously.
The application of nucleocapsid structure catalysis material, is also that by Gd2ErSbO7 powder be catalyst, or difference supporting Pt, NiO and RuO
2cocatalyst, light source is xenon lamp or high-pressure sodium lamp, in the airtight glass piping interior lighting reactor by multiple valve controls, carries out decomposition water hydrogen making.Scheme is preferably: 20% or 30% mass ratio of interpolation is (with Gd
3-xer
xsbO
7catalyst granules) NiO or RuO
2particle or powder and Gd
3-xer
xsbO
7evenly mixed.
(2) adopt X-ray diffractometer (XRD) to carry out material phase analysis to the invention described above catalyst; Adopt transmission electron microscope (TEM) to analyze the microstructure characteristic of the invention described above catalyst; Utilize ESEM (SEM) to carry out tissue topography's analysis to the invention described above catalyst, and in conjunction with ESEM power spectrum (SEM-EDS) and x-ray photoelectron power spectrum (XPS) measured they become to be grouped into, disclosed the electron structure feature of catalyst surface.Profound level has disclosed the microstructure of novel photocatalyst to the rule that affects of photocatalysis degradation organic contaminant efficiency.
Titan yellow in degraded water body under visible ray (or ultraviolet light) irradiates, aniline blue, the green B of diaminourea, core fast red, Ponceau S, in the process of the persistent organic pollutants such as methylene blue, by liquid chromatography/mass spectrometry (LC/MS) combined instrument and ion chromatograph, intermediate product and the end product of degrading in above-mentioned organic pollution process have been followed the tracks of in test, obtain under the effect of nucleus-shell magnetic coupling catalyst granules, the possible approaches of Some Organic Pollutants in degraded water body under visible ray (or ultraviolet light) irradiates, disclose titan yellow in water body, aniline blue, the green B of diaminourea, core fast red, Ponceau S, the degradation mechanism of the organic pollutions such as methylene blue.
Adopt single wavelength visible ray (or ultraviolet light) to irradiate titan yellow in water body, aniline blue, the green B of diaminourea, core fast red, Ponceau S, the organic pollutions such as methylene blue, successfully derive by experimental study and theoretical calculating photogenerated charge (light induced electron or the photohole) quantity that participates in photocatalytic degradation reaction, and then derive participate in reaction visible ray (or ultraviolet light) number of photons, in conjunction with the total number of photons of the incident light calculating, finally draw titan yellow in the water body of degrading under single wavelength visible ray (or ultraviolet light) effect, aniline blue, the green B of diaminourea, core fast red, Ponceau S, the photo-quantum efficiency of the organic pollutions such as methylene blue.
Table 1Gd
2erSbO
7atomic Structure Parameters
Table 2Gd
2feSbO
7xPS collection of illustrative plates in the combination energy peak value (eV) of each essential element
(3) .Gd
2erSbO
7performance characterization
Learn Gd by XRD, XPS result
2erSbO
7for single-phase, and experiment original material height is pure, without any impurity phase.
Measure Gd by Xray fluorescence spectrometer
2erSbO
7average atom molar percentage be Gd:Er:Sb:O=2.00:1.01:0.99:6.98.With Rietveld software to Gd
2erSbO
7xRD result carry out structure refinement, structure refinement factor R
pvalue is R
p=11.30%.Gd
2erSbO
7space group be Fd-3m, structure is cubic system, pyrochlore constitution, cell parameter a is
gd
2erSbO
7the indices of crystallographic plane such as (222), (400) of each diffraction maximum, (440), (622), (444), (800), (662), (840), (844) are demarcated.Gd
2erSbO
7in the space atom site parameter of each atom determined (in table 1).Adopt UV-vis DRS spectrometer to Gd
2erSbO
7the characteristic absorption limit producing under the irradiation of light is measured, and obtains Gd
2erSbO
7band gap width be 2.53eV, obtain Gd
2erSbO
7band structure, conduction band is made up of 4d track, the 5d track of Gd and the 5p track of Sb of Er, valence band is made up of the 2p track of O.Under radiation of visible light, with Gd
2erSbO
7for catalyst, crystal violet (C
25h
30clN
3) initial concentration be 0.0293mM, initial soln 300mL, radiation of visible light is after 200 minutes, the clearance of crystal violet is 97.39%, degraded crystal violet photo-quantum efficiency be 0.04996%; After radiation of visible light 240 minutes, the clearance of crystal violet is 100%.After radiation of visible light 200 minutes, crystal violet concentration changes with time dynamics Changshu K
cfor 0.0151min
-1; Crystal violet total organic carbon concentration changes with time dynamics Changshu K
tOCfor 0.0131min
-1; After radiation of visible light 200 minutes, CO
2spill-out be 0.2102mmol, the clearance of total organic carbon is 96.30%.
Application example
1. adopt Gd
2erSbO
7titan yellow (C in powder degrading waste water
28h
19n
5na
2o
6s
4)
By Gd
2erSbO
7powder 0.8g, puts into the 300mL titan yellow aqueous solution and forms suspension system, and the initial concentration of the titan yellow aqueous solution is 0.03mmol L
-1, initial pH value is 7.The xenon lamp of choosing 300W irradiates titan yellow solution, mixes edge filter (λ >420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, maintain catalyst fines by the mode of magnetic stirring apparatus and oxygenic aeration and be suspended state.Whole illumination reaction carries out under airtight lighttight environment.With Gd
2erSbO
7powder is catalyst, under radiation of visible light, along with the prolongation of irradiation time, the concentration of titan yellow reduces gradually, and total organic carbon (TOC) concentration also reduced gradually, through 320 minutes, the clearance of titan yellow is 100%, and the clearance (mineralization rate) of total organic carbon TOC reaches 99.52%, CO
2productive rate be 0.25012mmol, first order kinetics Changshu K of titan yellow concentration and time
cfor 0.02182min
-1, first order kinetics Changshu K of total organic carbon and time
tOCfor 0.01324min
-1.Detailed data are in table 3.
Table 3 is with Gd
2erSbO
7the related data that powder obtains for catalyst degradation titan yellow
2. adopt γ-Fe
2o
3(ferromagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7titan yellow (C in (photochemical catalyst shell) degrading waste water
28h
19n
5na
2o
6s
4)
Utilize homemade magnetic field-light-catalyzed reaction system, by the adjustable alternating magnetic field generator of magnetic field intensity, magnetic field intensity is chosen 0.5～5T (tesla).Light source is 300W xenon lamp.Adopt γ-Fe
2o
3(ferromagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7(photochemical catalyst shell), as catalyst, the percent by volume of above-mentioned three kinds of magnetic coupling catalysis materials respectively accounts for 1/3rd, selects the titan yellow of typical difficult degradation in water as target degradation product.In the time that magnetic field intensity is 2.5～3.2 tesla, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in the aqueous solution that contains titan yellow, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Now select the 900mL titan yellow aqueous solution, the Gd that all magnetic-particles surface applies simultaneously
2erSbO
7weight approaches 2.4g, and the initial concentration of the titan yellow aqueous solution is 0.03mmol L
-1, initial pH value is 7.The xenon lamp of choosing 300W irradiates titan yellow solution, mixes edge filter (λ >420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, adopt equally oxygenic aeration.Whole illumination reaction carries out under airtight lighttight environment.Finally apply flexibly magnetostatic field and alternating magnetic field, can make the surface coated photochemical catalyst of magnetic-particle fully contact with organic pollution and light source.Result shows with γ-Fe
2o
3(magnetic-particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of titan yellow reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 300 minutes, the clearance of titan yellow reaches 100%, and the clearance (mineralization rate) of total organic carbon TOC reaches 99.55%, CO
2productive rate be 0.24867mmol, first order kinetics Changshu K of titan yellow concentration and time
cfor 0.02592min
-1, first order kinetics Changshu K of total organic carbon and time
tOCfor 0.01469min
-1.Detailed data are in table 4.
Table 4 adopts γ-Fe
2o
3-Gd
2erSbO
7, SiO
2-Gd
2erSbO
7and MnO-Gd
2erSbO
7the related data obtaining for catalyst degradation titan yellow
3. adopt Gd
2erSbO
7aniline blue (C in powder degrading waste water
32h
25n
3na
2o
9s
3)
By Gd
2erSbO
7powder 0.8g, puts into the 300mL aniline blue aqueous solution and forms suspension system, and the initial concentration of the aniline blue aqueous solution is 0.03mmol L
-1, initial pH value is 7.The xenon lamp of choosing 300W irradiates aniline blue solution, mixes edge filter (λ >420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, maintain catalyst fines by the mode of magnetic stirring apparatus and oxygenic aeration and be suspended state.Whole illumination reaction carries out under airtight lighttight environment.With Gd
2erSbO
7powder is catalyst, under radiation of visible light, along with the prolongation of irradiation time, the concentration of aniline blue reduces gradually, and total organic carbon (TOC) concentration also reduced gradually, through 370 minutes, the clearance of aniline blue is 100%, and the clearance (mineralization rate) of total organic carbon TOC reaches 99.54%, CO
2productive rate be 0.28467mmol, first order kinetics Changshu K of aniline blue concentration and time
cfor 0.01572min
-1, first order kinetics Changshu K of total organic carbon and time
tOCfor 0.00938min
-1.Detailed data are in table 5.
Table 5 is with Gd
2erSbO
7the related data that powder obtains for catalyst degradation aniline blue
4. adopt γ-Fe
2o
3(ferromagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7aniline blue (C in (photochemical catalyst shell) degrading waste water
32h
25n
3na
2o
9s
3)
Utilize homemade magnetic field-light-catalyzed reaction system, by the adjustable alternating magnetic field generator of magnetic field intensity, magnetic field intensity is chosen 0.5～5T (tesla).Light source is 300W xenon lamp.Adopt γ-Fe
2o
3(ferromagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7(photochemical catalyst shell), as catalyst, the percent by volume of above-mentioned three kinds of magnetic coupling catalysis materials respectively accounts for 1/3rd, selects the aniline blue of typical difficult degradation in water as target degradation product.In the time that magnetic field intensity is 2.5～3.2 tesla, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in the aqueous solution that contains aniline blue, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Now select the 900mL aniline blue aqueous solution, the Gd that all magnetic-particles surface applies simultaneously
2erSbO
7weight approaches 2.4g, and the initial concentration of the aniline blue aqueous solution is 0.03mmol L
-1, initial pH value is 7.The xenon lamp of choosing 300W irradiates aniline blue solution, mixes edge filter (λ >420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, adopt equally oxygenic aeration.Whole illumination reaction carries out under airtight lighttight environment.Finally apply flexibly magnetostatic field and alternating magnetic field, can make the surface coated photochemical catalyst of magnetic-particle fully contact with organic pollution and light source.Result shows with γ-Fe
2o
3(magnetic-particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of aniline blue reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 350 minutes, the clearance of aniline blue reaches 100%, and the clearance (mineralization rate) of total organic carbon TOC reaches 99.57%, CO
2productive rate be 0.28497mmol, first order kinetics Changshu K of aniline blue concentration and time
cfor 0.01681min
-1, first order kinetics Changshu K of total organic carbon and time
tOCfor 0.01022min
-1.Detailed data are in table 6.
Table 6 adopts γ-Fe
2o
3-Gd
2erSbO
7, SiO
2-Gd
2erSbO
7and MnO-Gd
2erSbO
7the related data obtaining for catalyst degradation aniline blue
5. adopt Gd
2erSbO
7methylene blue (C in powder degrading waste water
16h
18clN
3s)
By Gd
2erSbO
7powder 0.8g, puts into 300mL aqueous solution of methylene blue and forms suspension system, and the initial concentration of aqueous solution of methylene blue is 0.03mmol L
-1, initial pH value is 7.The xenon lamp of choosing 300W irradiates methylene blue solution, mixes edge filter (λ >420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, maintain catalyst fines by the mode of magnetic stirring apparatus and oxygenic aeration and be suspended state.Whole illumination reaction carries out under airtight lighttight environment.With Gd
2erSbO
7powder be catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of methylene blue reduces gradually, total organic carbon (TOC) concentration also reduces gradually, and through 390 minutes, the clearance of methylene blue was 100%, the clearance (mineralization rate) of total organic carbon TOC reaches 99.55%, CO
2productive rate be 0.14187mmol, first order kinetics Changshu K of methylene blue concentration and time
cfor 0.01544min
-1, first order kinetics Changshu K of total organic carbon and time
tOCfor 0.00861min
-1.Detailed data are in table 7.
Table 7 is with Gd
2erSbO
7the related data that powder obtains for catalyst degradation methylene blue
6. adopt γ-Fe
2o
3(ferromagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7methylene blue (C in (photochemical catalyst shell) degrading waste water
16h
18clN
3s)
Utilize homemade magnetic field-light-catalyzed reaction system, by the adjustable alternating magnetic field generator of magnetic field intensity, magnetic field intensity is chosen 0.5～5T (tesla).Light source is 300W xenon lamp.Adopt γ-Fe
2o
3(ferromagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7(photochemical catalyst shell), as catalyst, the percent by volume of above-mentioned three kinds of magnetic coupling catalysis materials respectively accounts for 1/3rd, selects the methylene blue of typical difficult degradation in water as target degradation product.In the time that magnetic field intensity is 1.9～2.6 tesla, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in the aqueous solution that contains methylene blue, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Now select 900mL aqueous solution of methylene blue, the Gd that all magnetic-particles surface applies simultaneously
2erSbO
7weight approaches 2.4g, and the initial concentration of aqueous solution of methylene blue is 0.03mmol L
-1, initial pH value is 7.The xenon lamp of choosing 300W irradiates methylene blue solution, mixes edge filter (λ >420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, adopt equally oxygenic aeration.Whole illumination reaction carries out under airtight lighttight environment.Finally apply flexibly magnetostatic field and alternating magnetic field, can make the surface coated photochemical catalyst of magnetic-particle fully contact with organic pollution and light source, result shows with γ-Fe
2o
3(magnetic-particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of methylene blue reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 360 minutes, the clearance of methylene blue reaches 100%, and the clearance (mineralization rate) of total organic carbon TOC reaches 99.56%, CO
2productive rate be 0.14302mmol, first order kinetics Changshu K of methylene blue concentration and time
cfor 0.01673min
-1, first order kinetics Changshu K of total organic carbon and time
tOCfor 0.00963min
-1.Detailed data are in table 8.
Table 8 adopts γ-Fe
2o
3-Gd
2erSbO
7, SiO
2-Gd
2erSbO
7and MnO-Gd
2erSbO
7the related data obtaining for catalyst degradation methylene blue
7. adopt Gd
2erSbO
7green B (the C of diaminourea in powder degrading waste water
34h
22n
8na
2o
10s
2)
By Gd
2erSbO
7powder 0.8g, puts into the green B aqueous solution of 300mL diaminourea and forms suspension system, and the initial concentration of the green B aqueous solution of diaminourea is 0.03mmol L
-1, initial pH value is 7.The xenon lamp of choosing 300W irradiates the green B solution of diaminourea, mixes edge filter (λ >420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, maintain catalyst fines by the mode of magnetic stirring apparatus and oxygenic aeration and be suspended state.Whole illumination reaction carries out under airtight lighttight environment.With Gd
2erSbO
7powder be catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of the green B of diaminourea reduces gradually, total organic carbon (TOC) concentration also reduces gradually, and through 310 minutes, the clearance of the green B of diaminourea was 100%, the clearance (mineralization rate) of total organic carbon TOC reaches 99.58%, CO
2productive rate be 0.30293mmol, first order kinetics Changshu K of the green B concentration of diaminourea and time
cfor 0.01987min
-1, first order kinetics Changshu K of total organic carbon and time
tOCfor 0.01147min
-1.Detailed data are in table 9.
Table 9 is with Gd
2erSbO
7the related data that powder obtains for the green B of catalyst degradation diaminourea
8. adopt γ-Fe
2o
3(ferromagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7green B (the C of diaminourea in (photochemical catalyst shell) degrading waste water
34h
22n
8na
2o
10s
2)
Utilize homemade magnetic field-light-catalyzed reaction system, by the adjustable alternating magnetic field generator of magnetic field intensity, magnetic field intensity is chosen 0.5～5T (tesla).Light source is 300W xenon lamp.Adopt γ-Fe
2o
3(ferromagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7(photochemical catalyst shell), as catalyst, the percent by volume of above-mentioned three kinds of magnetic coupling catalysis materials respectively accounts for 1/3rd, selects the green B of diaminourea of typical difficult degradation in water as target degradation product.In the time that magnetic field intensity is 1.9～2.6 tesla, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in the aqueous solution that contains the green B of diaminourea, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Now select the green B aqueous solution of 900mL diaminourea, the Gd that all magnetic-particles surface applies simultaneously
2erSbO
7weight approaches 2.4g, and the initial concentration of the green B aqueous solution of diaminourea is 0.03mmol L
-1, initial pH value is 7.The xenon lamp of choosing 300W irradiates the green B solution of diaminourea, mixes edge filter (λ >420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, adopt equally oxygenic aeration.Whole illumination reaction carries out under airtight lighttight environment.Finally apply flexibly magnetostatic field and alternating magnetic field, can make the surface coated photochemical catalyst of magnetic-particle fully contact with organic pollution and light source, result shows with γ-Fe
2o
3(magnetic-particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of the green B of diaminourea reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 280 minutes, the clearance of the green B of diaminourea reaches 100%, and the clearance (mineralization rate) of total organic carbon TOC reaches 99.65%, CO
2productive rate be 0.30287mmol, first order kinetics Changshu K of the green B concentration of diaminourea and time
cfor 0.0219min
-1, first order kinetics Changshu K of total organic carbon and time
tOCfor 0.01297min
-1.Detailed data are in table 10.
Table 10 adopts γ-Fe
2o
3-Gd
2erSbO
7, SiO
2-Gd
2erSbO
7and MnO-Gd
2erSbO
7the related data obtaining for the green B of catalyst degradation diaminourea
9. adopt Gd
2erSbO
7core fast red (C in powder degrading waste water
14h
8nNaO
7s)
By Gd
2erSbO
7powder 0.8g, puts into the 300mL core fast red aqueous solution and forms suspension system, and the initial concentration of the core fast red aqueous solution is 0.03mmol L
-1, initial pH value is 7.The xenon lamp of choosing 300W irradiates core fast red solution, mixes edge filter (λ >420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, maintain catalyst fines by the mode of magnetic stirring apparatus and oxygenic aeration and be suspended state.Whole illumination reaction carries out under airtight lighttight environment.With Gd
2erSbO
7powder be catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of core fast red reduces gradually, total organic carbon (TOC) concentration also reduces gradually, and through 300 minutes, the clearance of core fast red was 100%, the clearance (mineralization rate) of total organic carbon TOC reaches 99.54%, CO
2productive rate be 0.12456mmol, first order kinetics Changshu K of core fast red concentration and time
cfor 0.02133min
-1, first order kinetics Changshu K of total organic carbon and time
tOCfor 0.01235min
-1.Detailed data are in table 11.
Table 11 is with Gd
2erSbO
7the related data that powder obtains for catalyst degradation core fast red
10. adopt γ-Fe
2o
3(ferromagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7core fast red (C in (photochemical catalyst shell) degrading waste water
14h
8nNaO
7s)
Utilize homemade magnetic field-light-catalyzed reaction system, by the adjustable alternating magnetic field generator of magnetic field intensity, magnetic field intensity is chosen 0.5～5T (tesla).Light source is 300W xenon lamp.Adopt γ-Fe
2o
3(ferromagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7(photochemical catalyst shell), as catalyst, the percent by volume of above-mentioned three kinds of magnetic coupling catalysis materials respectively accounts for 1/3rd, selects the core fast red of typical difficult degradation in water as target degradation product.In the time that magnetic field intensity is 1.9～2.6 tesla, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in the aqueous solution that contains core fast red, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Now select the 900mL core fast red aqueous solution, the Gd that all magnetic-particles surface applies simultaneously
2erSbO
7weight approaches 2.4g, and the initial concentration of the core fast red aqueous solution is 0.03mmol L
-1, initial pH value is 7.The xenon lamp of choosing 300W irradiates core fast red solution, mixes edge filter (λ >420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, adopt equally oxygenic aeration.Whole illumination reaction carries out under airtight lighttight environment.Finally apply flexibly magnetostatic field and alternating magnetic field, can make the surface coated photochemical catalyst of magnetic-particle fully contact with organic pollution and light source, result shows with γ-Fe
2o
3(magnetic-particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of core fast red reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 280 minutes, the clearance of core fast red reaches 100%, and the clearance (mineralization rate) of total organic carbon TOC reaches 99.65%, CO
2productive rate be 0.12439mmol, first order kinetics Changshu K of core fast red concentration and time
cfor 0.02359min
-1, first order kinetics Changshu K of total organic carbon and time
tOCfor 0.01456min
-1.Detailed data are in table 12.
Table 12 adopts γ-Fe
2o
3-Gd
2erSbO
7, SiO
2-Gd
2erSbO
7and MnO-Gd
2erSbO
7the related data obtaining for catalyst degradation core fast red
11. adopt Gd
2erSbO
7ponceau S (C in powder degrading waste water
22h
12n
4na
4o
13s
4)
By Gd
2erSbO
7powder 0.8g, puts into the 300mL Ponceau S aqueous solution and forms suspension system, and the initial concentration of the Ponceau S aqueous solution is 0.03mmol L
-1, initial pH value is 7.The xenon lamp of choosing 300W irradiates Ponceau S solution, mixes edge filter (λ >420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, maintain catalyst fines by the mode of magnetic stirring apparatus and oxygenic aeration and be suspended state.Whole illumination reaction carries out under airtight lighttight environment.With Gd
2erSbO
7powder be catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of Ponceau S reduces gradually, total organic carbon (TOC) concentration also reduces gradually, and through 240 minutes, the clearance of Ponceau S was 100%, the clearance (mineralization rate) of total organic carbon TOC reaches 99.53%, CO
2productive rate be 0.19582mmol, first order kinetics Changshu K of Ponceau S concentration and time
cfor 0.02750min
-1, first order kinetics Changshu K of total organic carbon and time
tOCfor 0.01636min
-1.Detailed data are in table 13.
Table 13 is with Gd
2erSbO
7the related data that powder obtains for catalyst degradation Ponceau S
12. adopt γ-Fe
2o
3(ferromagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7ponceau S (C in (photochemical catalyst shell) degrading waste water
22h
12n
4na
4o
13s
4)
Utilize homemade magnetic field-light-catalyzed reaction system, by the adjustable alternating magnetic field generator of magnetic field intensity, magnetic field intensity is chosen 0.5～5T (tesla).Light source is 300W xenon lamp.Adopt γ-Fe
2o
3(ferromagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7(photochemical catalyst shell), as catalyst, the percent by volume of above-mentioned three kinds of magnetic coupling catalysis materials respectively accounts for 1/3rd, selects the Ponceau S of typical difficult degradation in water as target degradation product.In the time that magnetic field intensity is 1.9～2.6 tesla, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in the aqueous solution that contains Ponceau S, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Now select the 900mL Ponceau S aqueous solution, the Gd that all magnetic-particles surface applies simultaneously
2erSbO
7weight approaches 2.4g, and the initial concentration of the Ponceau S aqueous solution is 0.03mmol L
-1, initial pH value is 7.The xenon lamp of choosing 300W irradiates Ponceau S solution, mixes edge filter (λ >420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, adopt equally oxygenic aeration.Whole illumination reaction carries out under airtight lighttight environment.Finally apply flexibly magnetostatic field and alternating magnetic field, can make the surface coated photochemical catalyst of magnetic-particle fully contact with organic pollution and light source, result shows with γ-Fe
2o
3(magnetic-particle core)-Gd
2erSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle core)-Gd
2erSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2erSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of Ponceau S reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 210 minutes, the clearance of Ponceau S reaches 100%, and the clearance (mineralization rate) of total organic carbon TOC reaches 99.68%, CO
2productive rate be 0.19559mmol, first order kinetics Changshu K of Ponceau S concentration and time
cfor 0.03289min
-1, first order kinetics Changshu K of total organic carbon and time
tOCfor 0.02060min
-1.Detailed data are in table 14.
Table 14 adopts γ-Fe
2o
3-Gd
2erSbO
7, SiO
2-Gd
2erSbO
7and MnO-Gd
2erSbO
7the related data obtaining for catalyst degradation Ponceau S
13. adopt Gd
2erSbO
7decomposition water hydrogen making
In the airtight glass piping interior lighting reactor by multiple valve controls, carry out the experiment of decomposition water hydrogen making, (incident flux is 4.76 × 10 to the xenon lamp of radiation source employing 300W
-6einstein L
-1s
-1, 420nm edge filter) or 400W(incident flux be 6.01 × 10
-6einstein L
-1s
-1, 390nm edge filter) high-pressure sodium lamp, in 300mL (16.65mol) pure water, put into Gd
2erSbO
7powder 0.8g.The hydrogen yield overflowing adopts with the gas chromatograph-mass spectrometer (GC-MS) of TCD and measures, and this gas chromatograph-mass spectrometer (GC-MS) is connected with airtight loop interior lighting reactor.Before reaction, in airtight loop interior lighting reactor, various gas is removed, and argon gas is charged this reactor, until the oxygen in reactor and nitrogen are completely removed.Under xenon lamp irradiates, after 24 hours, the output of hydrogen is 1673.4 micromoles, and the output of oxygen is 836.2 micromoles; Under high voltage mercury lamp radiation, after 24 hours, the output of hydrogen is 2789.8 micromoles, and the output of oxygen is 1393.7 micromoles.
With Gd
2erSbO
7powder is catalyst, supporting Pt respectively, NiO and RuO
2cocatalyst decomposition water hydrogen making, incident light dominant wavelength is λ=360nm, catalyst 0.8g, pure water 300mL, 50mL CH
3oH, light source is 400W high-pressure sodium lamp, with 0.2wt%-Pt/Gd
2erSbO
7for composite catalyst, after 24 hours, the output of hydrogen is 5.12mmol; With 1.0wt%-NiO/Gd
2erSbO
7for composite catalyst, after 24 hours, the output of hydrogen is 3.69mmol; With 1.0wt%-RuO
2/ Gd
2feSbO
7for composite catalyst, after 24 hours, the output of hydrogen is 2.96mmol, and detailed data are in table 15 and table 16.
Table 15 is with Gd
2erSbO
7powder is catalyst, the related data that decomposition water hydrogen making obtains under UV-irradiation
Table 16 is with Gd
2erSbO
7powder is catalyst, the related data that decomposition water hydrogen making obtains under radiation of visible light
Claims (1)
1. the preparation method of the catalysis material magnetic-particle of nucleocapsid structure, is characterized in that the catalysis material magnetic-particle of nucleocapsid structure is core-Gd
3-xer
xsbO
7, comprise γ-Fe
2o
3ferromagnetic particle core-Gd
3-xer
xsbO
7photochemical catalyst shell, 0.5≤x≤1, SiO
2paramagnetic particle core-Gd
3-xer
xsbO
7photochemical catalyst shell, 0.5≤x≤1, MnO anti-ferromagnetism granular core-Gd
3-xer
xsbO
7photochemical catalyst shell, 0.5≤x≤1; γ-Fe
2o
3, SiO
2with the particle diameter of MnO be 0.06-1 micron, Gd
3-xer
xsbO
7after parcel core, particle diameter is 0.09-1.30 micron;
Core-Gd
3-xer
xsbO
7preparation method: adopt the method for electrostatic interaction to prepare the catalysis material magnetic-particle of nucleocapsid structure complex microsphere: the Gd modifying by lotus positive electricity ethylene-acrylic rubber AEM
3-xer
xsbO
7ferromagnetic particle γ-Fe with bear electricity
2o
3, paramagnetic particle SiO
2or anti-ferromagnetism particle MnO interacts;
Adopt micron-sized powder photocatalytic material Gd
3-xer
xsbO
7, AEM, Nanoscale Iron magnetic-particle γ-Fe
2o
3, paramagnetic particle SiO
2or anti-ferromagnetism particle MnO; By powder photocatalytic material Gd
3-xer
xsbO
7quality 2-5 nanometer γ-Fe doubly
2o
3, SiO
2or the water that MnO is placed in respectively 500-1000 part quality stirs, add weak aqua ammonia 1-8 part, make nanometer γ-Fe
2o
3, SiO
2or MnO bear electricity, for subsequent use; Get 0.1g powder photocatalytic material Gd
3-xer
xsbO
7, with the ethanolic solution dipping stirring of AEM concentration 2-9%w/w, make Gd
3-xer
xsbO
7lotus positive electricity, then use the nanometer γ-Fe of above-mentioned configuration
2o
3, SiO
2or the mixed stirring of MnO ammoniacal liquor mixed solution is swelling, makes electronegative nanometer γ-Fe
2o
3, SiO
2or MnO is by the Gd of the AEM modification of electrostatic interaction and lotus positive electricity
3-xer
xsbO
7at Gd
3-xer
xsbO
7surface forms shell structure, and the thickness of shell is according to the nanometer γ-Fe adding
2o
3, SiO
2or the amount of MnO decides, and then use absolute ethyl alcohol successively, deionized water cyclic washing, remove unnecessary AEM ethanolic solution and ammonia spirit, room temperature is dried, and must have the catalysis material magnetic-particle core-Gd of nucleocapsid structure
3-xer
xsbO
7.
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|---|---|---|---|---|
| CN101797500A (en) * | 2009-12-31 | 2010-08-11 | 南京大学 | Gd3-xBixSbO7, Gd3-xYxSbO7 and In2BiTaO7 photocatalyst as well as preparation and application |
| CN102139209A (en) * | 2011-02-23 | 2011-08-03 | 南京大学 | Core-shell gadolinium indium antimony base composite magnetic-particle photochemical catalyst as well as preparation and application thereof |
| CN102139210A (en) * | 2011-02-23 | 2011-08-03 | 南京大学 | Gadolinium-ytterbium-stibium based composite magnetic particle photocatalyst with core-shell structure, preparation and application |
| CN102151563A (en) * | 2011-02-23 | 2011-08-17 | 南京大学 | Gadolinium-yttrium-antimony based composite magnetic particle photo catalyst of core-shell structure, preparation and application thereof |
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| CN101797500A (en) * | 2009-12-31 | 2010-08-11 | 南京大学 | Gd3-xBixSbO7, Gd3-xYxSbO7 and In2BiTaO7 photocatalyst as well as preparation and application |
| CN102139209A (en) * | 2011-02-23 | 2011-08-03 | 南京大学 | Core-shell gadolinium indium antimony base composite magnetic-particle photochemical catalyst as well as preparation and application thereof |
| CN102139210A (en) * | 2011-02-23 | 2011-08-03 | 南京大学 | Gadolinium-ytterbium-stibium based composite magnetic particle photocatalyst with core-shell structure, preparation and application |
| CN102151563A (en) * | 2011-02-23 | 2011-08-17 | 南京大学 | Gadolinium-yttrium-antimony based composite magnetic particle photo catalyst of core-shell structure, preparation and application thereof |
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| Elaboration et etude structurale des antimoniates de terres rares Ln2Ln′SbO7(Ln, Ln′ = Lu, Y, Gd, ou Ga) a l"aide de la sonde ponctuelle Eu3+;J.P.FAURIE et al;《Journal of Solid State Chemistry》;19761231;第17卷;7-14 * |
| J.P.FAURIE et al.Elaboration et etude structurale des antimoniates de terres rares Ln2Ln′SbO7(Ln, Ln′ = Lu, Y, Gd, ou Ga) a l"aide de la sonde ponctuelle Eu3+.《Journal of Solid State Chemistry》.1976,第17卷第7-14页. |
| Jingfei Luan et al.Structural Property and Catalytic Activity of New In2YbSbO7 and Gd2YbSbO7 Nanocatalysts under Visible Light Irradiation.《J.Phys.Chem.C》.2010,第114卷第9398-9407页. |
| Structural Property and Catalytic Activity of New In2YbSbO7 and Gd2YbSbO7 Nanocatalysts under Visible Light Irradiation;Jingfei Luan et al;《J.Phys.Chem.C》;20100429;第114卷;9398-9407 * |
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